CN101512335B - Method for employing SEC-FTIR data to predict mechanical properties of polyethylene - Google Patents
Method for employing SEC-FTIR data to predict mechanical properties of polyethylene Download PDFInfo
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- CN101512335B CN101512335B CN2007800319104A CN200780031910A CN101512335B CN 101512335 B CN101512335 B CN 101512335B CN 2007800319104 A CN2007800319104 A CN 2007800319104A CN 200780031910 A CN200780031910 A CN 200780031910A CN 101512335 B CN101512335 B CN 101512335B
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- 238000000034 method Methods 0.000 title claims abstract description 127
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 title claims description 20
- 239000004698 Polyethylene Substances 0.000 title description 39
- -1 polyethylene Polymers 0.000 title description 39
- 229920000573 polyethylene Polymers 0.000 title description 39
- 239000000126 substance Substances 0.000 claims abstract description 266
- 238000012549 training Methods 0.000 claims abstract description 171
- 229920000642 polymer Polymers 0.000 claims abstract description 167
- 238000012360 testing method Methods 0.000 claims abstract description 20
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 claims description 59
- 239000002131 composite material Substances 0.000 claims description 45
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 18
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- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- 230000006353 environmental stress Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 230000002596 correlated effect Effects 0.000 abstract 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; rubber; leather
- G01N33/442—Resins, plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
Abstract
The present invention provides several methods of determining values of physical or chemical properties of polymers. In these methods, at least two polymer training samples are provided. Characteristics of the polymer microstructures of the training samples are correlated with values of physical or chemical properties of the training samples. These correlations are subsequently applied to the respective characteristics of polymer test samples in order to determine the values of physical or chemical properties of the test samples.
Description
Background of invention
The present invention relates to determine the method for polymer physics or chemical property numerical value.Traditionally, in order to measure the numerical value of specific physical or chemical property, need a certain amount of specific aggregation resin to make goods or sample; Then, the goods of generation or sample are tested to determine the numerical value of described physics or chemical property by the analysis test method of regulation subsequently.This method is loaded down with trivial details, and this is not only because make goods or needed time of sample, but also because carries out the required time of each analysis test method.Further, the classic method that depends on special test may need a large amount of polymkeric substance, often the amount that can produce more than small-scale research laboratory or pilot-plant equipment.
Therefore, exist the needs to the method for the expectation chemistry of measuring sample or physical property numerical value, this method only needs a spot of polymkeric substance to be used for analyzing.Further, this method should provide the physics of sample to be tested or the numerical value of chemical property, and does not make goods or sample.Also further, this method should be able to allow to determine the physics of sample or chemical property numerical value and not carry out the analytical test of described physics or chemical property.
On the other hand, need to determine fast the expectation chemistry of sample or the method for physical property numerical value.This is to determining that chemistry or physical property numerical value are useful, it need not to drop into goods or required time and the expense of sample that is used for subsequent analysis of making, also need not to drop into and carry out required time of analysis test method and expense, it depends on concrete test, may need a couple of days or several weeks to measure the value of each character.Use the method that quick feedback only can be provided with the small amount of polymer sample, can significantly reduce and be used to realize physics or the resin design of chemical property feature and cycle length of product development of expecting.Therefore, method of the present invention is at above demand.
Summary of the invention
The present invention discloses the method for a kind of definite polymer physics or chemical property numerical value.On the one hand, the invention provides a kind of method of determining at least a polymer sample physics or chemical property numerical value.Described at least a polymer sample have molecular weight distribution (molecular weight distribution, MWD) curve and short-chain branched distribution (short branching distribution, SCBD).At this on the one hand, determine that the method for at least a polymer sample physics or chemical property numerical value comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has MWD curve, SCBD and the known numeric value of physics or chemical property separately; B) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, determine that at least two weighting cross terms along the place of molecular weight separately of described MWD curve and described SCBD, each weighting cross term is determined by following every product: (1) described molecular weight separately; (2) at the weight fraction of described molecular weight separately; (3) at the short chain branch number of per 1000 carbon atoms of described molecular weight separately; C) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, draw the figure of each weighting cross term to the logarithm of described molecular weight separately; D) area separately determination step c) under every curve; E) each the area separately with at least two kinds of polymkeric substance training samples described in the step d) is associated with the known numeric value of described physics separately or chemical property; And f) with the described correlation application of step e) in the area separately of described at least a polymer sample, be used for determining the physics of described at least a polymer sample or the numerical value of chemical property.
In another aspect of this invention, described method relates to single-point and determines.Be that described weighting cross term is determined at unimodal molecular weight.At this on the one hand, the invention provides a kind of method of determining at least a polymer sample physics or chemical property numerical value.Described at least a polymer sample has molecular weight, at the weight fraction of molecular weight separately with at the short-chain branch number of per 1000 carbon atoms of molecular weight separately.This method comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has molecular weight, at the weight fraction of molecular weight separately, in the short-chain branch number of per 1000 carbon atoms of molecular weight and the known numeric value of physics separately or chemical property separately; B), determine that each weighting cross term is determined by following every product: (1) described molecular weight separately in the weighting cross term of molecular weight separately for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples; (2) at the weight fraction of described molecular weight separately; (3) at the short-chain branch number of per 1000 carbon atoms of described molecular weight separately; C) each the weighting cross term separately with at least two kinds of polymkeric substance training samples described in the step b) is associated with the known numeric value of described physics separately or chemical property; And d) with the correlation application of step c) in the weighting cross term of described at least a polymer sample, be used for determining the numerical value of described at least a polymer sample physics or chemical property.
And in another aspect of the present invention, stoechiometric process can be used for determining the numerical value of at least a polymer sample physics or chemical property.Described at least a polymer sample has MWD curve and SCBD.This method comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has the known numeric value of MWD curve, SCBD and physics separately or chemical property; B) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, determine that at least two weighting cross terms along the place of molecular weight separately of described MWD curve and described SCBD, each weighting cross term is determined by following every product: (1) described molecular weight separately; (2) at the weight fraction of described molecular weight separately; (3) at the short-chain branch number of per 1000 carbon atoms of described molecular weight separately; C) adopt the stoichiometry analysis, define the mathematical relation between each the weighting cross term of described physics separately or chemical property numerical value and described at least two kinds of polymkeric substance training samples; And d) the described mathematical relation of step c) is applied to described weighting cross term separately in the step b) of described at least a polymer sample, is used for determining the physics or the chemical property numerical value of described at least a polymer sample.
One different aspect, the invention provides a kind of physics that the tie molecule probability determines at least a polymer sample or method of chemical property numerical value used.For example, described at least a polymer sample has composite denseness, MWD curve and SCBD.The physics of described definite at least a polymer sample or the method for chemical property numerical value comprise: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has the known numeric value of composite denseness, MWD curve, SCBD and physics separately or chemical property; B) for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, determine that at two density items each density item uses described composite denseness, MWD curve and SCBD to determine at least along the place of molecular weight separately of described MWD curve and described SCBD; C) by the definite fluxing temperature separately of each the density item in the step b); D) determine the probability separately that tie molecule forms by each fluxing temperature in the step c); E) determine weighting tie molecule probability separately, each weighting tie molecule probability is determined by following every product: (1) is at the weight fraction of described molecular weight separately; (2) probability that tie molecule forms in the step d) of described molecular weight separately; F) for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, draw the figure of each weighting tie molecule probability to the described logarithm of molecular weight separately; G) the described area separately determination step f) under every curve; H) each the area separately with at least two kinds of polymkeric substance training samples in the step g) is associated with the known numeric value of described physics separately or chemical property; And i) with step h) described correlation application in the area separately of described at least a polymer sample, be used for determining the physics of described at least a polymer sample or the numerical value of chemical property.
The further aspect of the present invention is to adopt the single spot method of tie molecule probability.Be that described weighting tie molecule probability is determined at unimodal molecular weight.At this on the one hand, the invention provides a kind of method of determining at least a polymer sample physics or chemical property numerical value.Described at least a polymer sample has composite denseness, molecular weight and at the weight fraction of molecular weight separately.This method comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has composite denseness, molecular weight, in the weight fraction of molecular weight and the known numeric value of physics separately or chemical property separately; B) for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, use described composite denseness to determine tie molecule (2L
c+ L
a) smallest molecule length; C) by each 2L in the step b)
c+ L
aDetermine the probability separately that the tie molecule at molecular weight separately forms; D) determine weighting tie molecule probability separately, each weighting tie molecule probability is determined by following every product: (1) is at the weight fraction of molecular weight separately; (2) tie molecule at molecular weight separately forms probability in step c); E) each the tie molecule of the weighting separately probability with at least two kinds of polymkeric substance training samples in the step d) is associated with the known numeric value of described physics separately or chemical property; And f) with the described correlation application of step e) in the weighting tie molecule probability of described at least a polymer sample, be used for determining the numerical value of described at least a polymer sample physics or chemical property.Definition
In order to help those of ordinary skills to understand detailed description of the present invention, provide as giving a definition.DW/d Log M-weight fraction.ESCR-environmental stress crack resistance (Environmental Stress Crack Resistance), ASTMD1693.The full notch creep test of FNCT-(Full Notched Creep Test), ISO 16770.FTIR-FFIR (Fourier Transform-Infrared spectrophotometry).M or MW-molecular weight (Molecular weight).MWD-molecular weight distribution (Molecular wei ght distribution).M
n-number average MW.M
w-weight average MW.The intrinsic draw ratio of NDR-(Natural Draw Ratio), ASTM D638.NPT-breach pipe test (Notched Pipe Test), ISO 13479.PENT-Pennsylvania notched test (Pennsylvania Notched Test), ASTM F1473 measured in a few hours.PSP1-primary structure parameter 1 (Primary structure parameter 1); The figure area under a curve of weighting cross term and molecular weight is calculated divided by 100,000.PSP2-primary structure parameter 2 (Primary structure parameter 2); The figure area under a curve of weighting tie molecule probability and molecular weight multiply by 100 and calculates.P
TMOr the probability of P-tie molecule formation.The short-chain branched distribution of SCBD-.The short-chain branch number of per 1000 carbon atoms of SCB ' s-.The SEC-size exclusion chromatography; Also refer to gel permeation chromatography (GPC).SP-NCTL-single-point breach constant tension load (Single Notched Constant Tensile Load), ASTM D5397,30% surrender.Weighting cross term-molecular weight, at the weight fraction of molecular weight separately with at the product of the short-chain branch number of per 1000 carbon atoms of molecular weight separately; Also be shown as M*dW/d (Log M) * SCB.Weighting tie molecule probability-form the product of probability at the weight fraction of molecular weight with at the tie molecule of molecular weight separately; Also be shown as dW/d (Log M) * P
TM2L
c+ L
a-tie molecule smallest molecule length; L
cBe crystal layer thickness, L
aBe amorphous layer thickness.
The accompanying drawing summary
Fig. 1 has provided molecular weight distribution (MWD) curve of illustrative polyolefin copolymers and the figure of short-chain branched distribution (SCBD).
Fig. 2 has provided the figure of the weighting cross term of illustrative polyolefin copolymers to the molecular weight logarithm.
Fig. 3 provided two exemplary series of polyolefin copolymer the Log of 2.4MPa PENT (hour) to the figure of primary structure parameter 1 (PSP1).
The figure that Fig. 4 provides has set forth the composite denseness of exemplary homopolymer and the empirical relationship of weight-average molecular weight logarithm.
Fig. 5 has provided the MWD curve of illustrative polyolefin copolymers and the figure of each homopolymer and multipolymer density item on the MWD curve.
The figure that Fig. 6 provides has set forth the empirical relationship of polyethylene polymer fluxing temperature and density.
Fig. 7 has provided an aspect of the inventive method and has compared 2L with the document numerical value of report
c+ L
a(measuring with nm) is as the figure of density function.
Fig. 8 has provided the figure of two kinds of illustrative polyolefin copolymers weighting tie molecule probability to the molecular weight logarithm.
Fig. 9 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-1 and the figure of short-chain branched distribution (SCBD).
Figure 10 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-2 and the figure of short-chain branched distribution (SCBD).
Figure 11 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-3 and the figure of short-chain branched distribution (SCBD).
Figure 12 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-4 and the figure of short-chain branched distribution (SCBD).
Figure 13 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-5 and the figure of short-chain branched distribution (SCBD).
Figure 14 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-6 and the figure of short-chain branched distribution (SCBD).
Figure 15 has provided molecular weight distribution (MWD) curve of bimodal polyethylene polymer B M-7 and the figure of short-chain branched distribution (SCBD).
Figure 16 has provided the figure of the weighting cross term of bimodal polyethylene polymkeric substance training sample BM-1 to BM-7 to the molecular weight logarithm.
Figure 17 provided bimodal polyethylene polymkeric substance training sample BM-2 to BM-7 the Log of 2.4MPa PENT (hour) to the figure of PSP1.
Figure 18 has provided the figure of the weighting cross term of the polyethylene polymer training sample that uses the chromium-based catalysts generation to the molecular weight logarithm.
Figure 19 provided use polyethylene and ethylene copolymers training sample that chromium-based catalysts produces the Log of 2.4MPa PENT (hour) to the figure of PSP1.
Figure 20 provided bimodal polyethylene polymkeric substance training sample the Log of 2.4MPa PENT (hour) to the weighting cross term divided by 100,000 figure.
Figure 21 provided various polyethylene polymer training samples use the stoichiometry analysis the PENT of 2.4MPa prediction (hour) to the figure of the PENT that measures.
Figure 22 provided various polyethylene polymer training samples use the stoichiometry analysis the PENT of 2.4MPa prediction (hour) to the figure of the PENT that measures.
Figure 23 provided use polyethylene polymer training sample that the different catalysts system produces the Log of 2.4MPa PENT (hour) to the figure of PSP2.
Figure 24 provided the LogSP-NCTL that uses the polyethylene polymer training sample that the different catalysts system produces (hour) to the figure of PSP2.
Figure 25 has provided the figure of the NDR of the polyethylene polymer training sample that uses the generation of different catalysts system to PSP2.
Figure 26 provided bimodal polyethylene polymkeric substance training sample the Log of 2.4MPa PENT (hour) to the figure of weighting tie molecule probability.
Detailed Description Of The Invention
The present invention relates to determine the method for polymer physics or chemical property numerical value.Interested exemplary physical or chemical property include, but are not limited among the present invention: PENT, ESCR, SP-NCTL, NPT, FNCT, NDR, the impact of cantilever fine strain of millet formula, dart impact, charpy impact, puncture resistance or Elmendorf tearing strength.The PENT value can be measured under different condition, for example, for instance, 2.4MPa, 3.0MPa or 3.8MPa.
Method of the present invention is applicable to the polymkeric substance of all kinds, although this method is specially adapted to the semi-crystal polymkeric substance.The present invention is relevant with polyolefin with being described to, particularly Natene and multipolymer.Will be understood that, the invention is not restricted to various aspects and embodiment, the present invention includes that in the spirit and scope that can be included in instructions and appended claims all substitute, modification and equivalent in this general introduction.
The difference of polymer micro-structural, for example the MWD curve and the SCBD of given polymkeric substance can influence physics or chemical property that the sort of polymkeric substance produces.Therefore, in one aspect of the invention, can use the knowledge of each sample MWD curve and SCBD to measure the physics or the chemical property numerical value of sample in this described method.On the other hand, the method according to this invention further needs the compound resin density of polymer sample.
The MWD curve of polymkeric substance can be provided by the known any method of those of ordinary skills.A limiting examples measuring the analytical technology of polymer MW D curve is SEC or GPC.Naturally, as using in the disclosure, the MWD data can be provided the MWD curve of polymkeric substance and in the associated weight mark of each MW or the like data, it comprises commonly used that use this area, as M
wAnd M
n
Similarly, the SCBD of polymkeric substance can be provided by the known any method of those of ordinary skills.Technology can include, but are not limited to: and the temperature rise elution fractionation (temperature rising elution fractionation, TREF), nuclear magnetic resonance (NMR) and SEC-FTIR.Inherently, use as the disclosure, the SCBD of polymkeric substance can be provided at the short-chain branch number (SCB ' s) of each per 1000 carbon atom in MW place on the MWD curve.
The SEC-FTIR that provides the method for polymer MW D curve and SCBD to be to use stoichiometry to analyze, at U.S. Patent number 6,632,680 and U.S. Patent Application Serial Number 10/463,849 in describe, describedly be disclosed in this and introduce in full by reference.The advantage of the SEC-FTIR relevant with the inventive method is only to need polymkeric substance training sample in a small amount and polymer sample to be used for analyzing to measure MWD curve and SCBD.In one aspect of the invention, provide each test or each of training sample to be used to measure MWD curve and SCBD less than about 5 grams.On the other hand, provide less than about 1 gram and be used for analyzing.Further, provide less than about 100 milligrams.Further, compare with measuring method, but another advantage of the present invention is the physics or the chemical property of fast measuring sample with traditional test.The technology of use such as SEC-FTIR combines with method of the present invention, and the numerical value of physics or chemical property can be measured in less than three hours.On the other hand, physics or chemical property numerical value can be measured in less than two hours.And on the other hand, physics or chemical property numerical value can be measured in less than one hour.
Similarly, compound resin density can be measured with the known any method of those of ordinary skills.Analytical technology includes, but are not limited to: refractive index or according to the molded density (molded density) of ASTM D 1238.Compound resin density is that polymkeric substance is as a whole in the density at all molecular weight places.
Although method is described with " comprising (comprising) " each step,, method also can " be made up of this each step " or " being made up of this each step " basically.Primary structure parameter 1 (PSP1)
One aspect of the present invention provides a kind of method of measuring at least a polymer sample physics or chemical property numerical value, and described at least a polymer sample has molecular weight distribution (MWD) curve and short-chain branched distribution (SCBD).Described MWD curve and SCBD can measure by the known any analytical technology of those of ordinary skills, as SEC-FTIR.Described polymer sample also can be described as experiment sample or unknown sample.The method of measuring at least a polymer sample physics or chemical property numerical value comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has the known numeric value of MWD curve, SCBD and physics separately or chemical property; B) for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, be determined at along at least two weighting cross terms at the place of molecular weight separately of described MWD curve and described SCBD, each weighting cross term is measured by following every product: (1) is molecular weight separately; (2) at the weight fraction of molecular weight separately; (3) at the short-chain branch number of per 1000 carbon atoms of molecular weight separately; C), draw each the weighting cross term and the figure of the logarithm of molecular weight separately for each and at least a polymer sample of at least two kinds of polymkeric substance training samples; D) area separately determination step c) under every curve; E) each the area separately with at least two kinds of polymkeric substance training samples in the step d) is associated with the known numeric value of physics or chemical property separately; And f) with the correlation application of step e) in the area separately of described at least a polymer sample, be used to measure the numerical value of described at least a polymer sample physics or chemical property.
The method according to this invention provides at least two kinds of different polymkeric substance training samples.Training sample also can be described as check sample.Every kind of polymkeric substance training sample has known MWD curve and known SCBD.MWD curve and SCBD can use for example SEC-FTIR mensuration of aforesaid technology.With regard to illustrative polyolefin copolymers, Fig. 1 has illustrated the MWD curve and the SCBD of multipolymer.X-axis is the logarithm of molecular weight, and the left-hand side Y-axis is the weight fraction at each molecular weight, and the right-hand side Y-axis is the short-chain branch number (SCB ' s) of per 1000 carbon atoms.The graph data that shows as Fig. 1 can be provided at least two kinds of polymkeric substance training samples and at least a polymer sample.
Further, every kind of polymkeric substance training sample have separately interested physics or the known numeric value of chemical property.For example, at least two kinds of polymkeric substance training samples can be provided, and wherein every kind has the known numeric value at the PENT of 2.4MPa, and described PENT numerical value has used to be measured in advance to the analytical test separately of PENT.
At least two kinds of polymkeric substance training samples are used to method of the present invention.Yet alternatively, can use at least three kinds of training samples, at least four kinds of training samples, at least five kinds of training samples, at least ten kinds of training samples, at least ten five kinds of training samples or at least two ten kinds of training samples.The quantity that can be used for different training samples of the present invention there is not the concrete upper limit.Useful is, the similar and scope that training sample covers of training sample and polymer sample comprises polymer sample, but this is optional.Further, training sample can comprise a-type double or multisample more, being included in the influence of the experimental error in MWD curve and the SCBD test, and the influence of interested separately physics or chemical property.
For each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, can use the data separately of every kind of sample as shown in Figure 1 to measure the weighting cross term.The weighting cross term is molecular weight, at the weight fraction of molecular weight separately with at the product of the short-chain branch number of per 1000 carbon atoms of molecular weight (being M*dW/d (Log M) * SCB ' s) separately.Though do not attempt to be theoretically limited, the applicant thinks that a factor relevant with the polymkeric substance of the toughness with raising (as: anti tear, impact, puncture or stress cracking) is to have more short-chain branch at higher molecular weight.That is, under lower molecular weight, exist high-caliber branching for not significantly contribution of the toughness (for example characteristic such as PENT, SP-NCTL, dart impact etc.) that improves.More properly, the high short chain branch content that is present in MWD curve high molecular end can significantly improve the toughness of polymkeric substance.Once more, do not attempt to be theoretically limited, the applicant thinks that weighting cross term as defined above obtains the effect that has higher branch content on higher polymer molecule weight fraction.
According to an aspect of the present invention, along MWD curve and SCBD, need at least two weighting cross terms at molecular weight place separately.At each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, with each weighting cross term and the logarithm drawing of molecular weight separately.This illustrates at illustrative polyolefin copolymers in Fig. 2.Though need at least two weighting cross terms, having more cross terms in molecular weight ranges is useful to form the curve that shows as Fig. 2.Therefore, according to a further aspect of the invention, can use at least five weighting cross terms, at least ten weighting cross terms, at least two ten five weighting cross terms, at least five ten weighting cross terms or at least one hundred weighting cross terms.There is not the concrete upper limit to can be used for weighting cross term quantity of the present invention.More add to weigh cross term the more smooth curve that shows as Fig. 2 is provided.
For each and at least a polymer sample of at least two kinds of polymkeric substance training samples, every kind of sample is measured area under a curve separately.For example, measure the area under a curve of exemplary copolymers among Fig. 2.Then, the area separately under the curve of each of at least two kinds of polymkeric substance training samples is with interested physics or chemical property numerical value are relevant separately.In one aspect of the invention, every area under a curve by divided by 100,000 with first order calculation structural parameters 1 (PSP1).Fig. 3 has illustrated concrete physics or chemical property (being at the Log of the 2.4MPa PENT in the case) correlativity to the PSP1 of two exemplary polyolefin series copolymers.The result shows that have linear relationship between the logarithm of character interested and the PSP1 numerical value, it is subjected to branch's content influence of multipolymer macromolecule weight fraction.
Show as Fig. 3,, can measure the interested physics or the chemical property numerical value of described at least a polymer sample by with correlation application each area under at least a polymer sample curve.This method further illustrates among the embodiment 1-2 below.
Another aspect of the present invention provides a kind of method of measuring at least a polymer sample physics or chemical property numerical value, and described at least a polymer sample has molecular weight, at the weight fraction of each molecular weight with at the short-chain branch number of per 1000 carbon atoms of each molecular weight.These parameters can be measured by the known any analytical technology of those of ordinary skills by MWD curve and SCBD, as SEC-FTIR.The method of at least a polymer sample physics of this mensuration or chemical property numerical value comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has molecular weight, at the weight fraction of molecular weight separately, in the short-chain branch number of per 1000 carbon atoms of molecular weight and the known numeric value of physics separately or chemical property separately; B) for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, be determined at the weighting cross term of molecular weight separately, each weighting cross term is measured by following every product: (1) is molecular weight separately; (2) at the weight fraction of molecular weight separately; (3) at the short-chain branch number of per 1000 carbon atoms of molecular weight separately; C) each the weighting cross term separately with at least two kinds of polymkeric substance training samples described in the step b) is associated with the known numeric value of described physics separately or chemical property; And d) with the correlation application of step c) in the weighting cross term of described at least a polymer sample, to measure the numerical value of described at least a polymer sample physics or chemical property.
Said method is the single point assay of method shown in Fig. 1-3.In the method, for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, be determined at the single weighting cross term of unimodal molecular weight.Further specify this method by the following examples 3.
By Fig. 3 obviously as can be known: not every polymer type has identical correlativity between physics or chemical property and weighting cross term or PSP1.For example, different catalysts system (as chromium, Z-N, metallocene etc. or their combination) or each the polyolefin resin family that uses different production methods (for example slurry, solution, gas phase etc. or their combination) to produce may have different calibration curves, or with interested physics or the different relation of chemical property.
The further aspect according to the present invention, stoechiometric process can be used for measuring the physics or the chemical property numerical value of at least a polymer sample, and described at least a polymer sample has MWD curve and SCBD.This method comprises: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has the known numeric value of MWD curve, SCBD and physics separately or chemical property; B) for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, be determined at along at least two weighting cross terms at the place of molecular weight separately of described MWD curve and described SCBD, each weighting cross term is measured by following every product: (1) is molecular weight separately; (2) at the weight fraction of molecular weight separately; (3) at the short-chain branch number of per 1000 carbon atoms of molecular weight separately; C) adopt the stoichiometry analysis, define at least two kinds of polymkeric substance training samples each physics separately or the mathematical relation between chemical property numerical value and the weighting cross term; And d) for described at least a polymer sample, the mathematical relation of step c) is applied to the weighting cross term separately of step b), measure the physics or the chemical property numerical value of described at least a polymer sample.
When using identical or different antigravity system at least two kinds of polymkeric substance training samples of preparation and at least a polymer sample, can use this stoechiometric process.For example, this method different polyolefin resin family of can be used for using different catalysts system (as chromium, Z-N, metallocene etc. or their combination) or using different production methods (for example slurry, solution, gas phase etc. or their combination) to produce.
The stoichiometry analysis is also at U.S. Patent number 6,632,680 and U.S. Patent Application Serial Number 10/463,849 in describe.In the present invention, the stoichiometry analysis can be used for defining at least two kinds of polymkeric substance training samples each physics separately or the mathematical relation between chemical property numerical value and the weighting cross term.At least two kinds of polymkeric substance training samples are used for this one side of the present invention.Yet alternatively, can use at least three kinds of training samples, at least four kinds of training samples, at least five kinds of training samples, at least ten kinds of training samples, at least ten five kinds of training samples or at least two ten kinds of training samples.The quantity that can be used for these different training samples on the one hand of the present invention there is not the concrete upper limit.Further specify among this stoechiometric process embodiment 4-5 below.Primary structure parameter 2 (PSP2)
On the other hand, the invention provides a kind of method of measuring the physics or the chemical property numerical value of at least a polymer sample, described at least a polymer sample has composite denseness, MWD curve and SCBD.Described composite denseness can be measured by the known any analytical technology of aforesaid those of ordinary skills.The physics of at least a polymer sample of described mensuration or the method for chemical property numerical value comprise: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has the known numeric value of composite denseness, MWD curve, SCBD and physics separately or chemical property; B) for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, at at least two density items at molecular weight place separately, each density item uses described composite denseness, MWD curve and SCBD to measure to mensuration along described MWD curve and described SCBD; C) by each the density item mensuration fluxing temperature separately in the step b); D) measure the probability separately that tie molecule forms by each fluxing temperature in the step c); E) measure separately weighting tie molecule probability, each weighting tie molecule probability is measured by following every product: (1) is at the weight fraction of molecular weight separately; (2) probability that tie molecule forms in the step d) of molecular weight separately; F), draw each the weighting tie molecule probability and the figure of the logarithm of molecular weight separately for each and at least a polymer sample of at least two kinds of polymkeric substance training samples; G) area separately determination step f) under every curve; H) each the area separately with at least two kinds of polymkeric substance training samples in the step g) is associated with the known numeric value of physics or chemical property separately; And i) with step h) correlation application in the area separately of described at least a polymer sample, be used to measure the physics of described at least a polymer sample or the numerical value of chemical property.
Though do not attempt to be theoretically limited, but the applicant think have more multiple-limb-higher molecular weight fraction on than long-chain-force these chains to enter the amorphous areas of polymkeric substance and increase their possibilities thus as tie molecule, semi-crystalline polymer matrix is maintained together.These tie molecules can significantly improve the toughness character (as: anti tear, impact, puncture or stress cracking) of polymkeric substance.In this one side of the present invention, said method relates to the numerical value that uses the tie molecule probability to measure polymer sample physics or chemical property.
This method of the present invention adopts at least two kinds of different polymkeric substance training samples.Each polymkeric substance training sample has known composite denseness, known MWD curve and known SCBD.As preceding indication, composite denseness can be measured by ASTMD1238, and SEC-FTIR measures and MWD curve and SCBD for example can use.For illustrative polyolefin copolymers, Fig. 1 has illustrated the MWD curve and the SCBD of multipolymer.The graph data that Fig. 1 shows can be provided at least two polymkeric substance training samples and at least one polymer sample.Further, each polymkeric substance training sample has the known numeric value of interested separately physics or chemical property.For example, at least two polymkeric substance training samples can be provided, and each has the known PENT numerical value at 2.4MPa, and this PENT numerical value has used to be measured in advance to the analytical test separately of PENT.
At least two polymkeric substance training samples are used for method of the present invention.Yet, alternatively, can use at least three training samples, at least four training samples, at least five training samples, at least ten training samples, at least ten five training samples or at least two ten training samples.The quantity that can be used for different training samples of the present invention there is not the concrete upper limit.Useful is, the scope that similar polymer sample of training sample and training sample cover comprises polymer sample, but this is optional.Further, training sample can comprise a-type double or more sample, comprising the influence of the experimental error in composite denseness, MWD curve and the SCBD test, and the influence of interested separately physics or chemical property.
For each and at least a polymer sample of at least two kinds of polymkeric substance training samples, use composite denseness, MWD curve and SCBD, measure along MWD curve and SCBD at least two density items of molecular weight separately.In order to measure at least two density items, utilize the relation between density and the molecular weight.
The composite denseness of polymkeric substance can be dependent on the MWD curve of polymkeric substance and SCBD etc.In one aspect of the invention, use the empirical relationship between composite denseness and the molecular weight to measure each density item.For some homopolymer, high density polyethylene for example, composite denseness increase with molecular weight and reduce.Use one group narrow MWD homopolymer (polydispersity index is about 2.3), as at Jordens etc., POLYMER, disclosed in 41 (2000), 7175, can measure the empirical relationship between composite denseness and the molecular weight.The composite denseness that Fig. 4 has provided exemplary homopolymer---high density polyethylene---is to the figure of weight-average molecular weight logarithm.By this linear relationship between composite denseness and the molecular weight logarithm being applied to exemplary MWD curve shown in Figure 1, can be determined at the density item of each molecular weight.
For having the short chain branch that can further suppress density or the multipolymer of side chain, can proofread and correct the correlativity of Fig. 4.Based on they weight fractions separately, add be derived from Fig. 4 the density item with evaluation calculation density, the no short chain of this supposition branch.For example, suppose that multipolymer has the composite denseness of about 0.951g/mL, suppose that the bulk density of no short chain branch can be about 0.957g/mL, difference is about 0.006g/mL.Correction factor divided by SCB ' the s average among the SCBD, can be applicable to measure each density item of multipolymer based on this variation of composite denseness then.Can use the analytical technology of NMR for example or SEC-FTIR to measure SCB ' s average.For the exemplary copolymers among Fig. 1, SCB ' the s average of whole polymkeric substance is about 1.5.Therefore, on an average, this exemplary copolymers is at the density item of each molecular weight, for each short chain branch of per 1000 carbon atoms, reduces about 0.004g/mL (0.006 divided by 1.5).For simplicity, although incorrect, this supposition is on all SCB ' s levels and all molecular weight of whole M WD curve, and each short chain branch equates the inhibition of density.The MWD curve of this method key diagram 1 in Fig. 5.Cover reaching the standard grade of MWD curve among Fig. 5 and use the density correlativity of Fig. 4, and suppose it is homopolymer, promptly do not have short chain branch.The use correction factor that rolls off the production line, its based on the variation of composite denseness divided by SCB ' the s average among the SCBD, to measure the density item of multipolymer on whole M WD curve.From Fig. 5, can be determined at each multipolymer density item of MW separately.
According to an aspect of the present invention, need along MWD curve and SCBD at least two density items of molecular weight separately.Though need at least two density items, useful is to have more a plurality of density items in molecular weight ranges, in order to form curve shown in Figure 5 and correlativity.Therefore, according to a further aspect of the invention, can use at least five density items, at least ten density items, at least two ten five density items, at least five ten density items or at least one hundred density items.There is not the concrete upper limit to can be used for density item quantity of the present invention.More the multi-density item can provide more accurate correction factor and more accurate multipolymer densimetric curve, shows as Fig. 5.
Then, can be by each density item mensuration fluxing temperature separately.A kind of such method is to use the empirical relationship between fluxing temperature and the density, for example among Fig. 6 to shown in the polyethylene polymer.Data among this figure are from Patel etc., J.APPL.POLY.SCI, 60 (1996), 749; Mirabella etc., J.POLY.SCI., PARTB:POLYMER PHYSICS, 40 (2002), 1637; With Huang etc., J.POLY.SCI., PARTB:POLYMERPHYSICS, 28 (1990), 2007.For the curve fitting purpose, it is the point of 1.01g/mL that the applicant has specified in density.Use Fig. 6, can be from the MWD curve of Fig. 5 separately each density item of molecular weight measure separately fluxing temperature.
In one aspect of the invention, measure the probability that tie molecule separately forms by each fluxing temperature.A technology relates to and is determined at each crystal layer thickness (L of MW separately
c) and amorphous layer thickness (L
a), this technology is used fluxing temperature and gibbs-Tang Pusen (Gibbs-Thompson) equation of Fig. 6, and this equation is that those of ordinary skills learn easily.Purpose is not only and is measured L
cAnd L
a, but be determined at each 2L of MW separately
c+ L
a2L
c+ L
aUsually be understood as that it is the smallest molecule length of tie molecule, wherein said tie molecule is across amorphous layer and across two crystal layers.Fig. 7 has illustrated that the present invention measures the 2L as density function
c+ L
aThe method of (measuring) and 2L with nm
c+ L
aNumerical fitting is fairly good, as document Patel etc., Mirabella etc. and Huang etc. report.The reason of some deviation of this model prediction may be such fact: the numerical value that is in the news is to equal M
wMolecular weight on.
Owing to be determined at each 2L on the MW separately
c+ L
a, therefore can measure the probability of tie molecule formation and (be abbreviated as P or P
TM).At each MW separately, P
TMBe the molecule distance of crossing over greater than at that 2L of MW separately
c+ L
aProbability.Huang etc. are at J.MATERIALSCI., have described a kind of method in 23 (1988), 3648, calculate to have concrete molecular weight (M
w) molecule form the probability of tie molecule, it is by transversal apart from 2L
c+ L
a, use following equation:
Wherein
And r
2=(Dnl
2) above-mentioned symbol has following meaning: probability L=critical distance=2L that the P=tethers forms
c+ L
aL
c=lamellar spacing L
aThe chain elongation factor=the tygon of=amorphous layer thickness D=melt is that 6.8n=linking number=tygon is M
wIt is 0.153nm that/14l=connects length=tygon.
Can be used for being determined at each P or P of MW separately based on electrical form and/or computer method from fluxing temperature separately
TMNumerical value.The P that uses this method to calculate
TMThe value of numerical value and bibliographical information is well suitable, as reports such as Patel.This method is measured P
TMSome limitation can comprise P
TMCan not reflect in the semi-crystal polymkeric substance actual tie molecule concentration (promptly from the ring that tangles may also as tie point) separately.And these calculating only draw static tie molecule level, and do not comprise new frenulum chain (dynamically)---its formation is because because the lamella that distortion causes slip.
For each and at least a polymer sample of at least two kinds of polymkeric substance training samples, weighting tie molecule probability can use the data separately of each sample to measure.Weighting tie molecule probability is at the weight fraction and the P of molecular weight separately
TMThe product of---tie molecule at molecular weight separately forms probability---(is dW/d (LogM) * P
TM).
According to an aspect of the present invention, need be along MWD curve and SCBD at least two weighting tie molecule probability of molecular weight separately.To each and at least a polymer sample of at least two kinds of polymkeric substance training samples, draw every kind of weighting tie molecule probability to the figure of molecular weight logarithm separately.What Fig. 8 illustrated is two kinds of illustrative polyolefin copolymers.Though need at least two weighting tie molecule probability, useful is to have more probability items in molecular weight ranges, to form curve shown in Figure 8.Therefore, according to a further aspect of the invention, can use at least five weighting tie molecule probability, at least ten weighting tie molecule probability, at least two ten five weighting tie molecule probability, at least five ten weighting tie molecule probability or at least one hundred weighting tie molecule probability.There is not the concrete upper limit to can be used for weighting tie molecule probability quantity of the present invention.More add to weigh the tie molecule probability the more smooth curve that shows as Fig. 8 is provided.
For each and at least one polymer sample of at least two polymkeric substance training samples, measure each sample in area under a curve separately.For example, measure exemplary copolymers area under a curve in Fig. 8.Then, at least two polymkeric substance training samples each, the separately numerical value of the area separately under the curve with interested physics or chemical property or a plurality of character is associated.In one aspect of the invention, each area under a curve takes advantage of 100 with first order calculation structural parameters 2 (PSP2).In Fig. 8, the polymer sample PSP2 value with higher peak is 10.9, and the polymer sample PSP2 value that has than ebb is 9.8.Use at least two kinds of polymkeric substance training samples, also can be formed correlativity with the PSP2 value with the correlativity of concrete physics or chemical property.
By will with the separately area of correlation application under at least a polymer sample curve of area separately under at least two kinds of polymkeric substance training sample curves, can measure the physics interested of at least a polymer sample or the numerical value of chemical property.This method is further described among below the embodiment 6-8.
When using identical or different antigravity system at least two kinds of polymkeric substance training samples of preparation and at least a polymer sample, can use this method that relates to tie molecule.For example, this method different polyolefin resin family of can be used for using different catalysts system (for example chromium, Z-N, metallocene etc. or their combination) or using different production methods (for example slurry, solution, gas phase etc. or their combination) to produce.
The present invention provides a kind of method of measuring the physics or the chemical property numerical value of at least a polymer sample on the other hand, and described at least a polymer sample has composite denseness, molecular weight and at the weight fraction of molecular weight separately.These parameters can be measured by the known various analytical technologies of foregoing those of ordinary skills.The physics of at least a polymer sample of this mensuration or the method for chemical property numerical value comprise: at least two kinds of polymkeric substance training samples a) are provided, and every kind of training sample has composite denseness, molecular weight, in the weight fraction of molecular weight and the known numeric value of physics separately or chemical property separately; B), use described composite denseness to measure the smallest molecule length (2L of tie molecule for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples
c+ L
a); C) 2L of each from step b)
c+ L
aBe determined at the probability separately of the tie molecule formation of molecular weight separately; D) measure weighting tie molecule probability separately, each weighting tie molecule probability is measured by following every product: (1) is at the weight fraction of molecular weight separately; (2) probability that in step c), forms at the tie molecule of molecular weight separately; E) each the tie molecule of the weighting separately probability with at least two kinds of polymkeric substance training samples in the step d) is associated with the known numeric value of described physics separately or chemical property; And f) with the weighting tie molecule probability of the correlation application in the step e), with the physics of measuring described at least a polymer sample or the numerical value of chemical property at least a polymer sample.
Said method is the single point assay of the described method of Fig. 4-8.In the method, for each and at least a polymer sample of at least two kinds of polymkeric substance training samples, be determined at the single weighting tie molecule probability of unimodal molecular weight.At this on the one hand, composite denseness is reflected in the influence of short-chain branched and molecular weight in the whole polymkeric substance.Use the described correlativity of Fig. 7, can be by the mensuration of the composite denseness separately 2L separately of polymer sample
c+ L
aValue.The further explanation among below the embodiment 9 of this method.EXAMPLE Example 1
Table I list Mw, the composite denseness that uses seven kinds of (7) bimodal polyethylene polymkeric substance that Ziegler-Natta catalyst produces and the PENT that measures at 2.4MPa (hour).Fig. 9-the 15th, the MWD curve and the SCBD of these seven kinds of polymkeric substance training samples.These figure have shown the data of using the SEC-FTIR commercial measurement and the SCBD of match, as at U.S. Patent number 6,632,680 and U.S. Patent Application Serial Number 10/463,849 in describe.Because at the low weight mark of high molecular very, often be difficult to accurately measure at these SCB ' s of molecular weight separately.Use the method for discussing before for the weighting cross term of these seven kinds of training samples and produce the described curve of Figure 16.Figure 16 area under a curve reduces to BM-7 from polyethylene polymer resin B M-1.There is strong linear relationship between LogPENT value that Figure 17 has illustrated at these polymkeric substance and the PSP1.Because the BM-1 polymkeric substance is not set up PENT numerical value accurately, it is not drawn on Figure 17.Therefore, can be from the PENT value (the unknown or experiment sample) of the sample of identical bimodal polymers family by the correlation application among Figure 17 to the PSP1 value of sample is measured.Embodiment 2
Use chromium-based catalysts to produce five kinds of (5) unimodal polyethylene polymers.These polymkeric substance have from about 0.948 to about 0.950 composite denseness and about M of 260 to about 320kg/mol
wAlso provide these five kinds of polymkeric substance training samples at the PENT of 2.4MPa value, MWD curve and SCBD.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.Use the method for discussing before for the weighting cross term of these five kinds of training samples and produce the described curve of Figure 18.There is strong linear relationship between Log PENT value that Figure 19 has illustrated at these polymkeric substance and the PSP1.Therefore, can be from the PENT value of the sample of same polymer family by Figure 19 correlation application to the PSP1 value of sample is measured.Embodiment 3
The identical bimodal polyethylene polymkeric substance that embodiment 3 uses embodiment 1 to discuss.Table II list six kinds of (6) bimodal polyethylene polymkeric substance concrete molecular weight, the weight fraction of that molecular weight, the SCB ' of that molecular weight s and the PENT that measures at 2.4MPa (hour).Calculate each weighting cross term of these six kinds of training samples, divided by 100,000, and the PENT value drawing to measuring.Even use this single spot method (promptly only at a molecular weight, the LogM=6.05 place obtains data), Figure 20 also illustrates between LogPENT value and weighting cross term are divided by 100,000 and has strong linear relationship.Therefore, can be from the PENT numerical value of the sample of identical bimodal polymers family by Figure 20 correlation application is measured in the single weighting cross term of sample.Embodiment 4
Table III is listed a series of polyethylene polymers that use chromium base, Z-N and dual catalyst system to make and is used the PENT value and the PENT value measured of stoichiometry analysis in the 2.4MPa prediction.These data illustrate in Figure 21.The MWD curve and the SCBD of these polymkeric substance training samples are provided by SEC-FTIR.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.For each polymkeric substance training sample, measure weighting cross term separately along MWD curve and SCBD.Stoechiometric process is used to produce PENT numerical value and weighting cross term and subsequently and mathematical relation between the PSP1 or correlativity.The mathematical relation of Figure 21 example is independent of antigravity system and the method that is used to produce the polymkeric substance training sample.Therefore, can be by the stoichiometry analytical applications be measured the PENT value of sample in the PSP1 of sample value.Embodiment 5
Table IV is listed the use stoichiometry of a series of polyethylene polymers that use the manufacturing of different catalysts system and is analyzed in the PENT value of 2.4MPa prediction and the PENT value of measuring.These data illustrate in Figure 22.The MWD curve and the SCBD of these polymkeric substance training samples are provided by SEC-FTIR.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.For each polymkeric substance training sample, measure weighting cross term separately along MWD curve and SCBD.Stoechiometric process is used to produce PENT numerical value and weighting cross term and subsequently and mathematical relation between the PSP1 or correlativity.Mathematical relation shown in Figure 22 is independent of antigravity system and the method that is used to produce the polymkeric substance training sample.Therefore, can be by the stoichiometry analytical applications be measured the PENT value of sample in the PSP1 of sample value.Embodiment 6
In this embodiment, two kinds of different polymeric families of assessment.The unimodal polyethylene polymer of selecting five kinds (5) to use chromium-based catalysts to produce.These polymkeric substance have wide MWD; The average polydispersity index about 30 of five kinds of polymkeric substance.The bimodal polyethylene polymkeric substance of selecting six kinds (6) to use Ziegler-Natta catalyst to produce.The average polydispersity index of these bimodal polymers is about 17.Provide these 11 kinds of polymkeric substance training samples at the PENT of 2.4MPa numerical value, MWD curve and SCBD.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.Provide the composite denseness of 11 kinds of polymkeric substance training samples and its scope about 0.947 to about 0.957g/mL.The method of discussing before using for the weighting tie molecule probability of these 11 kinds of training samples produces similar to Fig. 8 example curve.Measure the area separately under the curve and multiply by 100 to calculate the numerical value of PSP2 separately of every kind of training sample.There is strong linear relationship in Figure 23 explanation between the Log of these polymkeric substance PENT value and PSP2, have nothing to do with the antigravity system that is used to produce the polymkeric substance training sample.Therefore, can use PENT the value similar or polymer sample that the different catalysts system produces by Figure 23 correlation application is measured in the PSP2 of sample value.Embodiment 7
In this embodiment, assess three kinds of different polymeric families: use chromium-based catalysts unimodal polyethylene polymer that produces and the polymkeric substance that uses Ziegler-Natta catalyst to produce, and the bimodal polyethylene polymkeric substance that uses Ziegler-Natta catalyst to produce.SP-NCTL value, MWD curve and the SCBD of these 15 kinds of (15) polymkeric substance training samples are provided.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.The composite denseness of 15 kinds of polymkeric substance training samples is provided, and its scope about 0.93 to about 0.96g/mL.Use the method for discussing before for the weighting tie molecule probability of these 11 kinds of training samples and produce the curve similar to Fig. 8 example.Measure the area separately under the curve and multiply by 100 to calculate the numerical value of PSP2 separately of every kind of training sample.There is strong linear relationship in Figure 24 explanation between the Log of these multipolymers SP-NCTL value and PSP2, have nothing to do with the antigravity system that is used to produce the polymkeric substance training sample.Further, these polymkeric substance are crossed over big composite denseness scope.Therefore, can use polymer sample SP-NCTL value similar or that the different catalysts system produces by Figure 24 correlation application is measured in the PSP2 of sample value.Embodiment 8
In this embodiment, five kinds of different polymeric families of assessment: the unimodal polyethylene polymer that uses chromium-based catalysts, Ziegler-Natta catalyst and metallocene catalyst to produce; With the bimodal polyethylene polymkeric substance that uses Ziegler-Natta catalyst and metallocene catalyst to produce.Typical case's application to these fluoropolymer resins includes, but are not limited to: blowing, tubing, geotechnique use with film and film.NDR value, MWD curve and the SCBD of these 38 kinds of (38) polymkeric substance training samples are provided.Though do not show MWD curve and SCBD data, this information example in Fig. 9-15 relevant with embodiment 1 provides.The composite denseness of 38 kinds of (38) polymkeric substance training samples is provided, and its scope about 0.91 to about 0.96g/mL.The method of discussing before using for the weighting tie molecule probability of these 38 kinds of training samples produces similar to Fig. 8 example curve.Measure the area separately under the curve and multiply by 100 to calculate the numerical value of PSP2 separately of every kind of training sample.There is strong linear relationship in Figure 25 explanation between the NDR of these polymkeric substance value and PSP2, have nothing to do with the antigravity system that is used to produce the polymkeric substance training sample.Further, these polymkeric substance are crossed over big composite denseness scope, and are used for various final uses application.Therefore, can use NDR the value similar or polymer sample that the different catalysts system produces by Figure 25 correlation application is measured in the PSP2 of sample value.Embodiment 9
| Resin | M w | Density | PENT(h) |
| (kg/mol) | (g/cm 3) | (2.4MPa) | |
| BM-1 | 320 | 0.947 | ＞6000 |
| BM-2 | 290 | 0.949 | 3028 |
| BM-3 | 291 | 0.951 | 1046.5 |
| BM-4 | 270 | 0.951 | 625.5 |
| BM-5 | 260 | 0.953 | 406 |
| BM-6 | 228 | 0.954 | 36.5 |
| BM-7 | 193 | 0.959 | 3 |
| Resin | LogM | dW/dLogM | SCB’s | PENT(h)，2.4MPa |
| BM-2 | 6.05 | 0.201 | 2.96 | 3028 |
| BM-3 | 6.05 | 0.197 | 2.76 | 1046 |
| BM-4 | 6.05 | 0.174 | 2.65 | 625 |
| BM-5 | 6.05 | 0.166 | 2.65 | 406 |
| BM-6 | 6.05 | 0.146 | 2.63 | 36 |
| BM-7 | 6.05 | 0.122 | 2.61 | 3 |
| The PENT (h) that measures | The PENT (h) of prediction | |
| BM-A | 3028 | 3034 |
| BM-B | 2877 | 3109 |
| BM-C | 3172 | 2963 |
| BM-D | 1047 | 1001 |
| BM-E | 1047 | 1001 |
| BM-F | 1047 | 1001 |
| BM-G | 37 | 192 |
| BM-H | 35 | 192 |
| BM-I | 38 | 192 |
| BM-J | 406 | 469 |
| BM-K | 386 | 474 |
| BM-L | 425 | 465 |
| BM-M | 3 | -184 |
| BM-N | 3 | -184 |
| BM-O | 3 | -184 |
| CR-A | 77 | 97 |
| CR-B | 69 | 100 |
| CR-C | 84 | 93 |
| CR-D | 374 | 483 |
| CR-E | 337 | 499 |
| CR-F | 411 | 466 |
| CR-G | 506 | 590 |
| CR-H | 455 | 615 |
| CR-I | 556 | 564 |
| CR-J | 839 | 691 |
| CR-K | 755 | 729 |
| CR-L | 923 | 652 |
| CR-M | 1395 | 1344 |
| CR-N | 1255 | 1413 |
| CR-O | 1534 | 1274 |
| Resin | LogM | dW/dLogM | Density | PENT(h)，2.4MPa |
| BM-2 | 5.7 | 0.350 | 0.9493 | 3028 |
| BM-3 | 5.7 | 0.336 | 0.9509 | 1046 |
| BM-4 | 5.7 | 0.317 | 0.9514 | 625 |
| BM-5 | 5.7 | 0.303 | 0.9527 | 406 |
| BM-6 | 5.7 | 0.268 | 0.9544 | 36 |
| BM-7 | 5.7 | 0.227 | 0.9594 | 3 |
Claims (35)
1. determine the physics of at least a polymer sample or the method for chemical property numerical value for one kind, described at least a polymer sample has molecular weight distribution MWD curve and short-chain branched distribution SCBD, and this method comprises:
A) provide at least two kinds of polymkeric substance training samples, every kind of training sample has the known numeric value of MWD curve, SCBD and physics separately or chemical property;
B) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, determine that along described MWD curve and described SCBD at least two weighting cross terms of molecular weight separately, each weighting cross term is determined by following every product:
(1) described molecular weight separately;
(2) at the weight fraction of described molecular weight separately; With
(3) at the short-chain branch number of per 1000 carbon atoms of described molecular weight separately;
C), draw the figure of the logarithm of each weighting cross term and described molecular weight separately for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples;
D) area separately determination step c) under every curve;
E) with the described at least two kinds of polymkeric substance training samples in the step d) each described area separately with described separately physics or the described known numeric value of chemical property be associated; With
F) with the correlation application of step e) in the described area separately of described at least a polymer sample, with the described physics of determining described at least a polymer sample or the numerical value of chemical property,
Wherein said MWD curve and described SCBD are analyzed by SEC-FTIR and obtain.
2. method according to claim 1, wherein said physics or chemical property are in the PENT of 2.4MPa value.
3. method according to claim 1, wherein said physics or chemical property are in the PENT of 3.8MPa value.
4. method according to claim 1, wherein said physics or chemical property are environmental stress crack resistance ESCR.
5. method according to claim 1, wherein said physics or chemical property are single-point breach constant tension load SP-NCTL.
6. method according to claim 1, wherein said physics or chemical property are breach pipe test NPT.
7. method according to claim 1, wherein said physics or chemical property are full notch creep test FNCT.
8. method according to claim 1, wherein said physics or chemical property are intrinsic draw ratio NDR.
9. method according to claim 1 wherein provides each and described at least a polymer sample less than described at least two kinds of polymkeric substance training samples of about 1 gram to be used for analyzing.
10. method according to claim 1, wherein the described area under curve described in the step d) by divided by 100,000 with first order calculation structural parameters 1PSP1.
11. determine the physics of at least a polymer sample or the method for chemical property numerical value for one kind, described at least a polymer sample has MWD curve and SCBD, it comprises:
A) provide at least two kinds of polymkeric substance training samples, every kind of training sample has the known numeric value of MWD curve, SCBD and physics separately or chemical property;
B) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, determine that along described MWD curve and described SCBD at least two weighting cross terms of molecular weight separately, each weighting cross term is determined by following every product:
(1) described molecular weight separately;
(2) at the weight fraction of described molecular weight separately; With
(3) at the short-chain branch number of per 1000 carbon atoms of described molecular weight separately;
C) adopt the stoichiometry analysis, define described at least two kinds of polymkeric substance training samples each described separately physics or the mathematical relation between chemical property numerical value and the described weighting cross term; With
D) the described mathematical relation of step c) is applied to the described weighting cross term separately of the step b) of described at least a polymer sample, with the described physics of determining described at least a polymer sample or the numerical value of chemical property,
Wherein said MWD curve and described SCBD are analyzed by SEC-FTIR and obtain.
12. method according to claim 11, wherein said physics or chemical property are in the PENT of 2.4MPa value.
13. method according to claim 11, wherein said physics or chemical property are in the PENT of 3.8MPa value.
14. method according to claim 11, wherein said physics or chemical property are environmental stress crack resistance ESCR.
15. method according to claim 11, wherein said physics or chemical property are single-point breach constant tension load SP-NCTL.
16. method according to claim 11, wherein said physics or chemical property are breach pipe test NPT.
17. method according to claim 11, wherein said physics or chemical property are full notch creep test FNCT.
18. method according to claim 11, wherein said physics or chemical property are intrinsic draw ratio NDR.
19. method according to claim 11 wherein provides each and described at least a polymer sample less than described at least two kinds of polymkeric substance training samples of about 1 gram to be used for analyzing.
20. method according to claim 11, wherein said at least two kinds of polymkeric substance training samples and described at least a polymer sample are used identical or different antigravity system preparation.
21. determine the physics of at least a polymer sample or the method for chemical property numerical value for one kind, described at least a polymer sample has composite denseness, MWD curve and SCBD, it comprises:
A) provide at least two kinds of polymkeric substance training samples, every kind of training sample has the known numeric value of composite denseness, MWD curve, SCBD and physics separately or chemical property;
B) for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples, determine that along described MWD curve and described SCBD at least two density items of molecular weight separately, each density item uses described composite denseness, described MWD curve and described SCBD to determine;
C) by the definite fluxing temperature separately of each the density item in the step b);
D) determine the probability separately that tie molecule forms by each fluxing temperature in the step c);
E) determine weighting tie molecule probability separately, each weighting tie molecule probability is determined by following every product:
(1) at the weight fraction of described molecular weight separately; With
(2) probability that tie molecule forms in the step d) of described molecular weight separately;
F), draw the figure of the logarithm of each weighting tie molecule probability and described molecular weight separately for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples;
G) area separately determination step f) under every curve;
H) with at least two kinds of polymkeric substance training samples in the step g) each area separately with described separately physics or the described known numeric value of chemical property be associated; With
I) with step h) correlation application in the described area separately of described at least a polymer sample, with the physics of determining described at least a polymer sample or the numerical value of chemical property,
Wherein said MWD curve and described SCBD are analyzed by SEC-FTIR and obtain.
22. method according to claim 21, wherein said physics or chemical property are in the PENT of 2.4MPa value.
23. method according to claim 21, wherein said physics or chemical property are in the PENT of 3.8MPa value.
24. method according to claim 21, wherein said physics or chemical property are environmental stress crack resistance ESCR.
25. method according to claim 21, wherein said physics or chemical property are single-point breach constant tension load SP-NCTL.
26. method according to claim 21, wherein said physics or chemical property are breach pipe test NPT.
27. method according to claim 21, wherein said physics or chemical property are full notch creep test FNCT.
28. method according to claim 21, wherein said physics or chemical property are intrinsic draw ratio NDR.
29. method according to claim 21 wherein provides each and described at least a polymer sample less than described at least two kinds of polymkeric substance training samples of about 1 gram to be used for analyzing.
30. method according to claim 21, wherein said at least two kinds of polymkeric substance training samples and described at least a polymer sample are used identical or different antigravity system preparation.
31. method according to claim 21, wherein area under a curve is multiplied by 100 with first order calculation structural parameters 2PSP2 in step g).
32. method according to claim 21, wherein definite use composite denseness of each density item of step b) and empirical relationship and the correction factor between the molecular weight, described correction factor is based on the variation of the described composite denseness average short-chain branch number divided by per 1000 carbon atoms among the SCBD.
33. method according to claim 21, wherein each fluxing temperature of step c) uses the empirical relationship of fluxing temperature and density to determine.
34. determine the physics of at least a polymer sample or the method for chemical property numerical value for one kind, described at least a polymer sample has molecular weight, at the weight fraction of molecular weight separately with at the short-chain branch number of per 1000 carbon atoms of molecular weight separately, it comprises:
A) provide at least two kinds of polymkeric substance training samples, every kind of training sample has molecular weight, at the weight fraction of molecular weight separately, in the short-chain branch number of per 1000 carbon atoms of molecular weight separately and the known numeric value of physics or chemical property separately;
B), determine that each weighting cross term is determined by following every product in the weighting cross term of molecular weight separately for each and described at least a polymer sample of at least two kinds of polymkeric substance training samples:
(1) described molecular weight separately;
(2) at the described weight fraction of described molecular weight separately; With
(3) at the described short-chain branch number of per 1000 carbon atoms of described molecular weight separately;
C) each the weighting cross term separately with at least two kinds of polymkeric substance training samples described in the step b) is associated with the known numeric value of described physics separately or chemical property; With
D) with the described weighting cross term of the correlation application in the step c) in described at least a polymer sample, with the physics of definite described at least a polymer sample or the numerical value of chemical property,
Wherein said weight fraction and described the analysis by SEC-FTIR at the short-chain branch number of per 1000 carbon atoms of molecular weight separately at molecular weight separately obtains.
35. determine the physics of at least a polymer sample or the method for chemical property numerical value for one kind, described at least a polymer sample has composite denseness, molecular weight and at the weight fraction of molecular weight separately, described method comprises:
A) provide at least two kinds of polymkeric substance training samples, every kind of training sample has composite denseness, molecular weight, in the weight fraction of molecular weight and the known numeric value of physics separately or chemical property separately;
B) for each and described at least a polymer sample of described at least two kinds of polymkeric substance training samples, use described composite denseness to determine the smallest molecule length 2L of tie molecule
c+ L
a
C) by each 2L in the step b)
c+ L
aDetermine probability separately in the tie molecule formation of described molecular weight separately;
D) definite weighting tie molecule probability separately, each weighting tie molecule probability is determined by following every product:
(1) at the described weight fraction of described molecular weight separately; With
(2) probability that in step c), forms at the tie molecule of described molecular weight separately;
E) with at least two kinds of polymkeric substance training samples in the step d) each the described tie molecule of weighting separately probability with described separately physics or the known numeric value of chemical property be associated; With
F) with the weighting tie molecule probability of the correlation application in the step e) in described at least a polymer sample, with the described physics of definite described at least a polymer sample or the numerical value of chemical property,
Wherein said weight fraction at molecular weight is separately analyzed by SEC-FTIR and is obtained.
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| PCT/US2007/072219 WO2008002969A2 (en) | 2006-06-27 | 2007-06-27 | Method for employing sec-ftir data to predict mechanical properties of polyethylene |
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Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2588352A1 (en) * | 2007-05-11 | 2008-11-11 | Nova Chemicals Corporation | Method to estimate pent values |
| US20110035193A1 (en) * | 2009-08-07 | 2011-02-10 | Chevron Phillips Chemical Company Lp | System and method for estimating density of a polymer |
| US8932975B2 (en) | 2010-09-07 | 2015-01-13 | Chevron Phillips Chemical Company Lp | Catalyst systems and methods of making and using same |
| US8492498B2 (en) | 2011-02-21 | 2013-07-23 | Chevron Phillips Chemical Company Lp | Polymer compositions for rotational molding applications |
| US20130325363A1 (en) | 2012-05-31 | 2013-12-05 | Chevron Phillips Chemical Company Lp | Controlling Melt Fracture in Bimodal Resin Pipe |
| US8895679B2 (en) | 2012-10-25 | 2014-11-25 | Chevron Phillips Chemical Company Lp | Catalyst compositions and methods of making and using same |
| US8937139B2 (en) | 2012-10-25 | 2015-01-20 | Chevron Phillips Chemical Company Lp | Catalyst compositions and methods of making and using same |
| US9034991B2 (en) | 2013-01-29 | 2015-05-19 | Chevron Phillips Chemical Company Lp | Polymer compositions and methods of making and using same |
| US8877672B2 (en) | 2013-01-29 | 2014-11-04 | Chevron Phillips Chemical Company Lp | Catalyst compositions and methods of making and using same |
| US8815357B1 (en) * | 2013-02-27 | 2014-08-26 | Chevron Phillips Chemical Company Lp | Polymer resins with improved processability and melt fracture characteristics |
| DE202013007588U1 (en) | 2013-08-24 | 2013-09-27 | Cetecom Gmbh | Device for locating electromagnetic interference radiation |
| US9156970B2 (en) | 2013-09-05 | 2015-10-13 | Chevron Phillips Chemical Company Lp | Higher density polyolefins with improved stress crack resistance |
| CA2834068C (en) | 2013-11-18 | 2020-07-28 | Nova Chemicals Corporation | Enhanced escr bimodal rotomolding resin |
| US9828451B2 (en) | 2014-10-24 | 2017-11-28 | Chevron Phillips Chemical Company Lp | Polymers with improved processability for pipe applications |
| CN106645662B (en) * | 2015-10-28 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of system and its application of environmental stress resistance performance that evaluating polyvinyl resin |
| CA2914166C (en) | 2015-12-08 | 2022-07-26 | Nova Chemicals Corporation | High density rotomolding resin |
| KR102095523B1 (en) * | 2016-11-24 | 2020-03-31 | 주식회사 엘지화학 | Method for predicting property of polymers |
| KR102097132B1 (en) * | 2016-11-24 | 2020-04-03 | 주식회사 엘지화학 | Assessment method for polyethylene resin |
| KR102068795B1 (en) * | 2016-11-24 | 2020-01-21 | 주식회사 엘지화학 | Method for predicting property of polymers |
| US11098139B2 (en) | 2018-02-28 | 2021-08-24 | Chevron Phillips Chemical Company Lp | Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins |
| US11628183B2 (en) | 2018-07-27 | 2023-04-18 | ARC Medical Ine. | Highly purified fucans for the treatment of fibrous adhesions |
| JP7227346B2 (en) * | 2019-03-05 | 2023-02-21 | エーアールシー メディカル デバイス，インク． | Method for Predicting Molecular Weight Distribution of Biopolymer Mixtures |
| US11453733B2 (en) | 2019-04-17 | 2022-09-27 | Chevron Phillips Chemical Company Lp | Polyolefin process monitoring and control |
| CA3158392A1 (en) | 2019-11-01 | 2021-05-06 | Nova Chemicals Corporation | Linear high-density polyethylene with high toughness and high escr |
| MX2022015085A (en) | 2020-06-11 | 2023-01-11 | Nova Chem Int Sa | Linear high-density ethylene interpolymer compositions. |
| US11674023B2 (en) * | 2020-10-15 | 2023-06-13 | Chevron Phillips Chemical Company Lp | Polymer composition and methods of making and using same |
| US11802865B2 (en) | 2021-12-27 | 2023-10-31 | Chevron Phillips Chemical Company Lp | Utilizing aTREF data with chemometric analysis for determining the types of polyethylene present in polymer blends and multilayer films |
| EP4332150A1 (en) * | 2022-09-05 | 2024-03-06 | Borealis AG | Method of blending polyethylene based blends |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0341091A2 (en) * | 1988-05-06 | 1989-11-08 | The Dow Chemical Company | Linear low density polyethylene of ultra low density |
| CN1264402A (en) * | 1997-06-20 | 2000-08-23 | 陶氏化学公司 | Ethylene polymer compositions and article fabricated from the same |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US515474A (en) * | 1894-02-27 | Pump foe inflating pneumatic tiees | ||
| FR2508047B1 (en) * | 1981-06-22 | 1985-10-11 | Bp Chimie Sa | PROCESS FOR TREATING LOW LINEAR DENSITY POLYETHYLENE WITH ORGANIC PEROXIDES, FREE RADICAL GENERATORS |
| US5071913A (en) * | 1987-12-11 | 1991-12-10 | Exxon Chemical Patents Inc. | Rubbery isoolefin polymers exhibiting improved processability |
| US5039614A (en) * | 1988-06-16 | 1991-08-13 | Armenag Dekmezian | Method and apparatus for collecting samples for analysis of chemical composition |
| US5151474A (en) | 1990-02-16 | 1992-09-29 | The Dow Chemical Company | Process control method for manufacturing polyolefin |
| US5675253A (en) * | 1991-11-20 | 1997-10-07 | Auburn International, Inc. | Partial least square regression techniques in obtaining measurements of one or more polymer properties with an on-line nmr system |
| US5700895A (en) * | 1993-08-23 | 1997-12-23 | Sumitomo Chemical Company, Limited | Ethylene-α-olefin copolymer and molded article thereof |
| US5631069A (en) | 1994-05-09 | 1997-05-20 | The Dow Chemical Company | Medium modulus molded material comprising substantially linear polyethlene and fabrication method |
| US6506866B2 (en) * | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
| US6072576A (en) * | 1996-12-31 | 2000-06-06 | Exxon Chemical Patents Inc. | On-line control of a chemical process plant |
| WO2001098700A1 (en) * | 2000-06-22 | 2001-12-27 | Idemitsu Petrochemical Co., Ltd. | Pipe made of ethylene polymer |
| US6632680B1 (en) * | 2000-09-22 | 2003-10-14 | Deslauriers Paul J. | Measurement of short chain branching in olefin copolymers using chemometric analysis |
| US7427506B2 (en) * | 2004-04-13 | 2008-09-23 | Exxonmobil Chemical Patents Inc. | High throughput property testing of olefin copolymers using rheological determinations |
-
2006
- 2006-06-27 US US11/476,339 patent/US7803629B2/en not_active Expired - Fee Related
-
2007
- 2007-06-27 ES ES07812367.6T patent/ES2536766T3/en active Active
- 2007-06-27 AU AU2007265111A patent/AU2007265111A1/en not_active Abandoned
- 2007-06-27 ES ES12156922.2T patent/ES2661580T3/en active Active
- 2007-06-27 WO PCT/US2007/072219 patent/WO2008002969A2/en active Application Filing
- 2007-06-27 CN CN2007800319104A patent/CN101512335B/en not_active Expired - Fee Related
- 2007-06-27 RU RU2009102541/15A patent/RU2009102541A/en not_active Application Discontinuation
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-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0341091A2 (en) * | 1988-05-06 | 1989-11-08 | The Dow Chemical Company | Linear low density polyethylene of ultra low density |
| CN1264402A (en) * | 1997-06-20 | 2000-08-23 | 陶氏化学公司 | Ethylene polymer compositions and article fabricated from the same |
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| CN101512335A (en) | 2009-08-19 |
| EP2469277B1 (en) | 2017-12-27 |
| EP2469277A1 (en) | 2012-06-27 |
| AU2007265111A1 (en) | 2008-01-03 |
| EP2038649B1 (en) | 2015-05-06 |
| US7803629B2 (en) | 2010-09-28 |
| ES2661580T3 (en) | 2018-04-02 |
| CA2655850A1 (en) | 2008-01-03 |
| WO2008002969A3 (en) | 2008-02-21 |
| US20070298508A1 (en) | 2007-12-27 |
| WO2008002969A2 (en) | 2008-01-03 |
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